A Study of the Driving Force for Inclusion Complexation of α- and β-Cyclodextrin with Substituted Benzene

Ｉｎｔｒｏｄｕｃｔｉｏｎα－Ｃｙｃｌｏｄｅｘｔｒｉｎａｎｄβ－ｃｙｃｌｏｄｅｘｔｒｉｎ（α－ａｎｄβ－ＣＤ）ａｒｅｍａｃｒｏｃｙｃｌｉｃｏｌｉｇｏｍｅｒｓｏｆｓｉｘａｎｄｓｅｖｅｎｇｌｕｃｏｓｅｕｎｉｔｓ，ｒｅｓｐｅｃｔｉｖｅｌｙ．Ｔｈｅｙｈａｖｅｂ...     

Crystal Structure of Ethyl Ester N－（Isopropylcarbamoyl－Methoxyphosphonyl）－（1）－α－Phenylalanine

ＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅｏｆＥｔｈｙｌＥｓｔｅｒＮ－（Ｉｓｏｐｒｏｐｙｌｃａｒｂａｍｏｙｌ－Ｍｅｔｈｏｘｙｐｈｏｓｐｈｏｎｙｌ）－（１）－α－ＰｈｅｎｙｌａｌａｎｉｎｅＣｈｅｎＲｕ－Ｙｕ；ＬｉＨｕｉ－Ｙｉｎｇ（ＩｎｓｔｉｔｕｔｅｏｆＥｌｅｍｅ...     

Crystal and Molecular Structure of N－Isopropyl－O－（p－Chlorophenyl）－O＇－（1，2：3，4－Di－O＂－isopropylidene－α－D－galactopyranosyl） Thiophosphoramidate

ＣｒｙｓｔａｌａｎｄＭｏｌｅｃｕｌａｒＳｔｒｕｃｔｕｒｅｏｆＮ－Ｉｓｏｐｒｏｐｙｌ－Ｏ－（ｐ－Ｃｈｌｏｒｏｐｈｅｎｙｌ）－Ｏ＇－（１，２：３，４－Ｄｉ－Ｏ＂－ｉｓｏｐｒｏｐｙｌｉｄｅｎｅ－α－Ｄ－ｇａｌａｃｔｏｐｙｒａｎｏｓｙｌ）Ｔｈｉｏｐｈｏｓｐｈ...     

Crystal Structure of 1，2：5，6－Di－O－isopropylidene－α－D－glucofuranosyl N，N－bis（2－chloroethyl） Phosphordiamidate

ＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅｏｆ１，２：５，６－Ｄｉ－Ｏ－ｉｓｏｐｒｏｐｙｌｉｄｅｎｅ－α－Ｄ－ｇｌｕｃｏｆｕｒａｎｏｓｙｌＮ，Ｎ－ｂｉｓ（２－ｃｈｌｏｒｏｅｔｈｙｌ）ＰｈｏｓｐｈｏｒｄｉａｍｉｄａｔｅＣｈｅｎＲｕ－Ｙｕ；ＣｈｅｎＸｉａｏ－Ｒｕ（...     

Crystal Structure of O，O－Diethyl－（α－p－Hydroxyphenyl－β－Nitroethyl）phosphonate

ＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅｏｆＯ，Ｏ－Ｄｉｅｔｈｙｌ－（α－ｐ－Ｈｙｄｒｏｘｙｐｈｅｎｙｌ－β－Ｎｉｔｒｏｅｔｈｙｌ）ｐｈｏｓｐｈｏｎａｔｅＺｈａｎｇＸｉｎ（ＤｅｐａｒｔｍｅｎｔｏｆＣｈｅｍｉｓｔｒｙ，ＴｉａｎｊｉｎＥｄｕｃａｔｉｏｎＣｏｌｌｅ...     

Synthesis,Characterization and Catalytic Activity of Polyoxometalates Derived from α-P_2W_(15)O_56~(12

Ｓｙｎｔｈｅｓｉｓ,ＣｈａｒａｃｔｅｒｉｚａｔｉｏｎａｎｄＣａｔａｌｙｔｉｃＡｃｔｉｖｉｔｙｏｆＰｏｌｙｏｘｏｍｅｔａｌａｔｅｓＤｅｒｉｖｅｄｆｒｏｍα－Ｐ_２Ｗ_（１５）Ｏ_５６~（１２－）ＬｉｇａｎｄＭＥＮＧＬｕ,ａｎｄＬＩＵＪｉｎｇ－ｆｕ（Ｄｅｐａ...     

An SCF－MS－Xα Study of the Electronic Structures of Binuclear and Trinuclear Gold（Ⅰ） Compounds

ＡｎＳＣＦ－ＭＳ－ＸαＳｔｕｄｙｏｆｔｈｅＥｌｅｃｔｒｏｎｉｃＳｔｒｕｃｔｕｒｅｓｏｆＢｉｎｕｃｌｅａｒａｎｄＴｒｉｎｕｃｌｅａｒＧｏｌｄ（Ⅰ）ＣｏｍｐｏｕｎｄｓＧＵＯＣｈｕｎ－ｘｉａｏ（ＤｅｐａｒｔｍｅｎｔｏｆＣｈｅｍｉｓｔｒｙ，ＪｉｌｉｎＵｎｉｖ...     

Regioselechve Reaction of α－（Alkoxydimethylsilyl）allyl Carbanions with Alkyl Halides and Aldehydes

ＲｅｇｉｏｓｅｌｅｃｈｖｅＲｅａｃｔｉｏｎｏｆα－（Ａｌｋｏｘｙｄｉｍｅｔｈｙｌｓｉｌｙｌ）ａｌｌｙｌＣａｒｂａｎｉｏｎｓｗｉｔｈＡｌｋｙｌＨａｌｉｄｅｓａｎｄＡｌｄｅｈｙｄｅｓ￥ＬｉＬＩＵ；ＬａｂＨａｉＬＩ；ａｎｄＤｏｎｇＷＡＮＧ（Ｉｎｓｔｉｔｕｔ...     

Crystal Structure of O，O－Diethyl－α－（β－triphenylgermanyl）－propionoyloxy Methylphosphonate

ＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅｏｆＯ，Ｏ－Ｄｉｅｔｈｙｌ－α－（β－ｔｒｉｐｈｅｎｙｌｇｅｒｍａｎｙｌ）－ｐｒｏｐｉｏｎｏｙｌｏｘｙＭｅｔｈｙｌｐｈｏｓｐｈｏｎａｔｅＣｈｅｎＲｕ－Ｙｕ；ＭａｏＬｉ－Ｊｕａｎ；ＬｉｕＡｉ－Ｌｉｎ（Ｉｎｓｔｉｔｕｔｅｏ...     

Synthesis of （2E）－α，β－Unsaturated Amides Catalyzed by Micro Palladium Under Solid－Liquid Phase－Transfer Conditions

Ｓｙｎｔｈｅｓｉｓｏｆ（２Ｅ）－α,β－ＵｎｓａｔｕｒａｔｅｄＡｍｉｄｅｓＣａｔａｌｙｚｅｄｂｙＭｉｃｒｏＰａｌｌａｄｉｕｍＵｎｄｅｒＳｏｌｉｄ－ＬｉｑｕｉｄＰｈａｓｅ－ＴｒａｎｓｆｅｒＣｏｎｄｉｔｉｏｎｓＤＵＪｉｎ－ｘｉｎｇ（Ｄｅｐａｒｒｍｅｎｔｏ...     

黄花木化学成分研究

从黄花木中分离得到5种化合物,经化学和光谱方法鉴定它们为:野决明碱、安那吉碱、金雀花碱、β-谷甾醇及1新化合物5-α-羟基-7,17-脱氢异羽扇豆碱。研究结果表明,黄花木属、野决明属和沙冬青属植物在植物化学分类学上具有亲缘关系。     

(S)-(+)-姜黄烯的立体选择性全合成

利用不对称双羟化反应和Raney镍的原位还原,高对映选择性和高产率地实现了(S)-(+)-α-姜黄烯(1)的立体选择性合成.用MsCl保护化合物7a和7b时,发现了有趣的消除和重排反应,得到对应的二烯化合物8.     

(+)-菊花烯酮的Baeyer-Villiger反应

Baeyer-Villiger反应是酮在过氧酸氧化下形成酯的反应,是有机反应中合成酯的主要方法,这一反应可应用在环酮扩环形成含氧杂环内酯的反应上．由于反应是立体控制的,已广泛应用于天然产物,例如：抗生素、类固醇和信息素中间体的合成,某些用其它方法难以合成的羟基酸可由内酯水解得到。     

Evidence of steric factors in the fungitoxic mechanisms of 8-quinolinol and its 2-, 3-, 4-, 5-, 6-and 7-chloro and bromo analogues

Summary A study was made of the fungitoxicity of 2-, 3-, 4-, 5-, 6- and 7-chloro and bromo-8-quinolinols againstAspergillus niger,A. oryzae,Myrothecium verrucaria,Trichoderma viride andTrichophyton mentagrophytes in Sabouraud dextrose broth and in Yeast Nitrogen Base supplemented with 1%D-glucose and 0.088%L-asparagine. Based on the presence or absence of synergism between pairs of substituted 8-quinolinols and reversal or nonreversal of toxicity byL-cysteine or N-acetyl-L-cysteine, the following conclusions were reached: (1) substituents on the quinoline ring change the site(s) of action of the toxicant; (2) the sites of action of the 5-, 6-, and 7-chloro-8-quinolinols are different from each other and from 8-quinolinol and its 2-, 3-, and 4-chloro analogues, and the same is true for the corresponding bromo compounds; (3) 8-quinolinol and its 3- and 4-chloro and bromo analogues appear to share common sites of action; (4) for good antifungal activity the 2 position of the ring must not be substituted by sterically bulky groups; (5) the geometry of the binding sites of action are not so constrained that they cannot accommodate the analogously substituted chloro- and bromo-8-quinolinols.

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Nachweis sterischer Faktoren bei der Fungitoxizität von 8-Chinolinol und seinen 2-, 3-, 4-, 5-, 6- und 7-Chlor- und -Brom-Analogen

Zusammenfassung Es wurde eine Studie der Fungitoxizität von 2-, 3-, 4-, 5-, 6- und 7-Chlor- und-Brom-8-chinolinol gegenüberAspergillus niger,A. oryzae,Myrothecium verrucaria,Trichoderma viride undTrichphyton mentagrophytes in Sabouraud Dextrose Nährmedium und in Hefe-N-Base mit 1%D-Glucose und 0.088%L-Asparagin unternommen. Auf der Basis des Zutreffens oder der Abwesenheit eines Synergismus zwischen Paaren von substituierten 8-Chinolinolen und der Umkehrung oder Nichtumkehrung der Toxizität durchL-Cystein oder N-Acetyl-L-cystein wurden folgende Schlußfolgerungen abgeleitet: (1) Substituenten am Chinolin-Ring ändern die Aktionsstelle(n) des Toxikans; (2) Die Angriffsstellen der 5-, 6- und 7-Chlor-8-chinolinole sind untereinander und von 8-Chinolinol und seinen 2-, 3- und 4-Chlor-Analogen verschieden, wobei das auch für die entsprechenden Brom-Verbindungen gilt; (3) 8-Chinolinol und seine 3- und 4-Chlor- und -Brom-Analogen scheinen gemeinsame Aktionsstellen zu teilen; (4) für eine gute antifungale Aktivität darf die 2-Position des Rings nicht mit sterisch anspruchsvollen Gruppen besetzt sein; (5) Die Geometrie des Bindungsstellen der Wirkung ist nicht so gespannt, daß nicht sowohl analoge Chlor- oder Brom-8-chinolinole Platz finden.

     

Molecular structure and vibrational spectra of 4-, 5-, 6-chloroindole

The molecular geometry, IR intensities, harmonic and anharmonic vibrational frequencies of 4-, 5-, 6-chloroindole in the ground state were calculated by DFT/B3LYP level of theory using the 6-31G (d, p) basis set. To give complete and reasonable vibrational assignments, the normal coordinate analysis has been performed for 4-chloroindole, 5-chloroindole and 6-chloroindole. The effect of position of chloro atom on the molecular properties (electron density, dipole moments and energies) of the indole aromatic system is examined on the basis of calculation data for 4-, 5- and 6-chloroindoles.     

吡唑并[1,5-α]吡啶类化合物的合成及其体外受体结合分析

以吡唑并[1,5-α]吡啶-3-甲醛和N-甲酰基哌嗪为原料,经过还原胺化、水解和N-烷基化反应,合成了3-(4-苄基哌嗪-1-基甲基)吡唑并[1,5-α]吡啶、3-[4-(4-氯苄基)哌嗪-1-基甲基]吡唑并[1,5-α]吡啶和3-[4-(4-甲氧基苄基)哌嗪-1-基甲基]吡唑并[1,5-α]吡啶,通过1H NMR、ESI MS等技术手段对中间体及3个目标化合物进行了表征,并通过体外受体结合实验,测定3个目标化合物对多巴胺D4.2受体的亲和常数(Ki)分别为1.6、7.2、65 nmol/L;对D2受体的亲和常数分别为1920、5320和9800 nmol/L;对D3受体的亲和常数分别为1710、4270和5600 nmol/L。结果表明,3-(4-苄基哌嗪-1-基甲基)吡唑并[1,5-α]吡啶对多巴胺D4受体具有较高的亲和性与选择性,是多巴胺D4受体潜在的配基。     

Knockdown of 14-3-3ζ enhances radiosensitivity and radio-induced apoptosis in CD133+ liver cancer stem cells

14-3-3ζ is related to many cancer survival cellular processes. In a previous study, we showed that silencing 14-3-3ζ decreases the resistance of hepatocellular carcinoma (HCC) to chemotherapy. In this study, we investigated whether silencing 14-3-3ζ affects the radioresistance of cancer stem-like cells (CSCs) in HCC. Knockdown of 14-3-3ζ decreased cell viability and the number of spheres by reducing radioresistance in CSCs after γ-irradiation (IR). Furthermore, the levels of pro-apoptotic proteins were upregulated in CSCs via silencing 14-3-3ζ after IR. These results suggest that 14-3-3ζ knockdown enhances radio-induced apoptosis by reducing radioresistance in liver CSCs.     

Recyclable synthesis of mesityl iodonium(III) salts

An efficient protocol for C–H condensation of hypervalent iodine compounds toward arenes in fluoroalcohols has been applied to the recyclable preparation of mesityl iodonium(III) salts. The electrophilicities of [hydroxy(tosyloxy)iodo]mesitylene (MesI(OH)OTs) and iodomesitylene diacetate (MesI(OAc)₂) are suitably enhanced in 2,2,2-trifluoroethanol. A series of nucleophilic aromatic compounds react smoothly with MesI(OH)OTs and MesI(OAc)₂ or in situ hypervalent iodine(III) species, generated from iodomesitylene, to provide the target mesityl iodonium(III) salts in good yields at room temperature with broad functional group tolerance. This C–H condensation strategy merits high para-regioselectivities during the diaryliodonium(III) salt formation, but the major limitation in the case of low-reactive aromatic substrates is byproduct formation resulting from the self-condensation of the nucleophilic mesitylene ring in MesI(OH)OTs and MesI(OAc)₂.     

Coordination ability of insect kinin analogs

Spectroscopic data, including electronic absorption, CD and EPR results, as well as theoretical calculations have shown that the insertion of 4-aminopyroglutamate, a novel cis-peptide bond mimic, in the insect kinin peptide leads to an effective ligand towards Cu(II) ions at basic pH ranges. The 4-aminopyroglutamate motif induces a specific peptide conformation which favors the formation of one or two five-membered chelating rings stabilizing a bent structure, with the coordination of 3N-type or 4N-type in the metallopeptide molecule involving in metal bonding C-terminal of modified peptide. It is worth noting that the copper(II) bonding does not undergo hydrolysis even at a very high pH range.